CN102768954A - Polishing liquid for CMP and polishing method - Google Patents

Polishing liquid for CMP and polishing method Download PDF

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Publication number
CN102768954A
CN102768954A CN2012102257938A CN201210225793A CN102768954A CN 102768954 A CN102768954 A CN 102768954A CN 2012102257938 A CN2012102257938 A CN 2012102257938A CN 201210225793 A CN201210225793 A CN 201210225793A CN 102768954 A CN102768954 A CN 102768954A
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cmp
colloidal silica
lapping liquid
silica particles
grinding
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CN102768954B (en
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筱田隆
田中孝明
金丸真美子
天野仓仁
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • B24B37/04—Lapping machines or devices; Accessories designed for working plane surfaces
    • B24B37/042—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor
    • B24B37/044—Lapping machines or devices; Accessories designed for working plane surfaces operating processes therefor characterised by the composition of the lapping agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/31051—Planarisation of the insulating layers
    • H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The present invention can provide a polishing liquid for CMP having good dispersion stability and a high polishing rate in polishing of interlayer insulating films and a polishing method. Disclosed a polishing liquid for CMP comprising: a medium; and colloidal silica particles dispersed in the medium, wherein the colloidal silica particles satisfy the following conditions (1) to (3): (1) a two-axis average primary particle diameter (R1) obtained from images of twenty arbitrarily selected colloidal silica particles observed by a scanning electron microscope is within the range of 35 to 55 nm; (2) a value S1/S0 obtained by dividing a specific surface area (S1) of a colloidal silica particle measured by BET method by a calculated specific surface area (S0) of a true sphere having the same particle diameter as the two-axis average primary particle diameter (R1) determined by (1) above is 1.20 or less; and (3) a ratio, association degree: RS/R1, of a secondary particle diameter (RS) of the colloidal silica particles measured with a dynamic light scattering particle size distribution analyzer and the two-axis average primary particle diameter (R1) determined by (1) above in the polishing liquid for CMP is 1.30 or less.

Description

CMP is with lapping liquid and Ginding process
The present invention is that application number is the dividing an application for the invention application of " CMP is with lapping liquid and Ginding process " that 2009801132039 (international application no is PCT/JP2009/057641), the applying date be on April 16th, 2009, denomination of invention.
Technical field
The present invention relates to a kind of distribution at semiconductor device and form the CMP that is used to grind in the operation etc. with lapping liquid and Ginding process.
Background technology
In recent years, along with highly integrated, the high performance of semiconductor integrated circuit (following note is made LSI), new Micrometer-Nanometer Processing Technology also constantly is developed.Cmp (following note is made CMP) method is exactly one of them, and it is the technology of particularly in multilayer wired formation technology, often using in LSI manufacturing process, is used for the planarization of interlayer dielectric, the formation of metal plug, the formation of flush type distribution.This technology for example is disclosed in the patent documentation 1.
In addition, recently,, attempt utilizing copper and copper alloy as the conductive material that constitutes wiring material in order to make the LSI high performance.
But, copper or copper alloy be difficult to aluminium alloy distribution through in the past form in the frequent dry-etching method of using carry out miniaturization processing.
Therefore, main (damascene) method of inlaying that adopts, so-called inlaying process is meant, being pre-formed on the fluted dielectric film deposition and imbedding copper or copper alloy thin films, removes the said film beyond the groove through CMP, thereby forms the method for flush type distribution.This technology for example is disclosed in the patent documentation 2.
The usual method of grinding the metal CMP of conductive materials such as copper or copper alloy does; Grinding pad (being also referred to as abrasive cloth) is attached on the circular grinding price fixing (pressure nog plate); Surperficial with metal film on one side with lapping liquid dipping grinding pad; On one side with the face that is formed with metal film of substrate by the surface that is pressed in grinding pad, apply under the state of pressure (following note is made grinding pressure) of regulation the spin finishing price fixing to metal film at the back side from grinding pad; The metal film of protuberance is removed in the relative mechanical friction of the protuberance through lapping liquid and metal film.
The metal film that is used for CMP generally includes oxidant and polishing particles with lapping liquid, can also further add oxidized metal dissolving agent, diaphragm formation agent etc. as required.Think that basic mechanism is, at first through oxidant oxidation metallic film surface, again through this oxide layer of polishing particles grinding.
Because the oxide layer of the metal surface of recess less contacts with grinding pad, polishing particles does not have ground effect, so along with the carrying out of CMP, the metal level of protuberance is removed, makes the substrate surface planarization.About its details, for example be disclosed in the non-patent literature 1.
As the method for the grinding rate that improves CMP, it is effective adding oxidized metal dissolving agent.This is interpreted as, because when making the particle of the metal oxide of polishing particles grinding be dissolved in the lapping liquid (following note is done etching), the ground effect that polishing particles plays strengthens.
Through adding oxidized metal dissolving agent, the grinding rate of CMP is improved, still; On the other hand, the oxide layer of the metallic film surface of recess also is etched, and makes when metallic film surface is exposed; Oxidized dose of further oxidation of metallic film surface carried out so repeatedly, and the recess metal film is carried out etching.Therefore, after the grinding, the surperficial middle body of the metal wiring of imbedding produces as the sagging phenomenon of plate (following note is made dish and fallen into (dishing)), infringement planarization effect.
In order to prevent this situation, further add diaphragm and form agent.Diaphragm forms agent and on the oxide layer of metallic film surface, forms diaphragm, prevents that oxide layer from dissolving in lapping liquid.Hope that this diaphragm can be easily by the polishing particles grinding, and the grinding rate of CMP is reduced.
For the corrosion in falling into and grinding of the butterfly that suppresses copper or copper alloy; Form the high LSI distribution of reliability, advocate and use the method for CMP that be described below: contain as amion acetic acid such as the glycine of oxidized metal dissolving agent or acid amides sulfuric acid and as the BTA (BTA) of diaphragm formation agent with lapping liquid.This technology for example is recorded in the patent documentation 3.
On the other hand; Shown in Fig. 1 (a); By the lower floor of distributions such as copper or copper alloy, be formed with and be used for preventing that copper is to interlayer dielectric 1 diffusion with improve the layer (below be also referred to as the barrier layer) of the barrier metal 2 of adaptation with the formed conductive material 3 of metal level.As barrier metal 2, can use for example tantalum compounds such as tantalum, tantalum alloy, tantalum nitride etc.In CMP technology, the part beyond the wiring part of imbedding conductive material is necessary to remove the barrier metal 2 that exposes through CMP.
But because hardness ratio conductive material 3 height of these barrier metals 2, even therefore the grinding-material used of combination conductive material can not obtain sufficient grinding rate, and flatness can variation under a lot of situation.Therefore, worked out 2 sections such Ginding process, it comprises the 2nd operation of grinding barrier metal 2 of the 1st operation and the state from Fig. 1 (b) to Fig. 1 (c) of the grinding conductive material 3 of the state from Fig. 1 (a) to Fig. 1 (b).
In the 2nd grinding step that grinds barrier metal 2, in order to improve flatness, the part (overmastication) that also can grind the thickness of protuberance interlayer dielectric 1 usually.For interlayer dielectric 1; Silicon oxide film is a main flow; Yet in recent years,, attempt utilizing ratio silicon oxide film dielectric constant low silicon based material or organic polymer in order to make the LSI high performance; For example, with the trimethyl silane organic silicate glass and the full aromatic ring Low-k film etc. of initiation material as Low-k (low-k) film.
The prior art document
Patent documentation
Patent documentation 1: No. 4944836 specification of United States Patent (USP)
Patent documentation 2: No. 1969537 communique of Japan Patent
Patent documentation 3: No. 3397501 communique of Japan Patent
Non-patent literature
Non-patent literature 1: ジ ャ one Na Le オ Block エ レ Network ト ロ ケ ミ カ Le ソ サ エ テ ィ will (Journal of Electrochemical Society), 1991, the 138th volume, No. 11, p.3460～3464.
Summary of the invention
The problem that invention will solve
For time of shortening grinding step, enhance productivity, the grinding rate of barrier metal 2 and interlayer dielectric 1 is preferably at a high speed.In order to improve the grinding rate of interlayer dielectric 1, consideration for example improves CMP with the amount of the polishing particles in the lapping liquid, the particle diameter of polishing particles in the increase lapping liquid usually.
But in either case, dispersion stabilization all has the tendency of deterioration, and the sedimentation of polishing particles takes place easily.That is, use afterwards if preserve the regular hour to lapping liquid, such problem will occur: the grinding rate of interlayer dielectric reduces easily, can not obtain flatness.Therefore, people seek a kind of like this lapping liquid, its have with in the past barrier layer with the equal barrier layer grinding rate of lapping liquid, and the grinding rate of interlayer dielectric is also wanted enough soon.
Point in view of the above problems; The purpose of this invention is to provide a kind of CMP and use lapping liquid, this CMP is good with the dispersion stabilization of the polishing particles in the lapping liquid, can grind with the grinding rate of interlayer dielectric at a high speed; When keeping this characteristic, the grinding rate on barrier layer also is at a high speed.
In addition, another object of the present invention provides a kind of Ginding process, and it is used to make miniaturization, filmization, dimensional accuracy and the electrical characteristic with excellence, and the semiconductor device of the high and low cost of reliability etc.
The present invention has carried out various researchs in order to solve above-mentioned problem, and the result finds, uses colloidal silica particles as grinding, and following aspect is important factor: the average primary particle diameter of aforementioned colloidal silica particles is in the scope of regulation; Particle has the shape that is similar to positive spheroid; CMP be in lapping liquid a little can with state.
The means of dealing with problems
More specifically, the present invention finds:
CMP uses lapping liquid, contains medium and is dispersed in the colloidal silica particles in this aforementioned medium, and the full terms shown in (1)～(3) below aforementioned colloidal silica particles satisfies then has excellent characteristic:
(1) from the image that obtains through the aforementioned colloidal silica particles of scanning electron microscopy (SEM) observation, selects 20 particles arbitrarily, two average primary particle diameter (R of said 20 particles 1) be 35～55nm;
(2) have and two average primary particle diameter (R that in aforementioned (1), try to achieve 1) the specific area calculated value of positive spheroid of same particle size is (S 0), the specific area of the aforementioned colloidal silica particles of measuring through the BET method is (S 1), with (S 0) removal (S 1) resulting value (S 1/ S 0) be below 1.20;
(3) CMP with lapping liquid in, through the aggregate particle size (Rs) of the fixed aforementioned colloidal silica particles of dynamic light scattering mode particle size distribution instrumentation and two average primary particle diameter (R that in aforementioned (1), try to achieve 1) ratio (degree of association: Rs/R 1) be below 1.30.In addition, use lapping liquid with respect to the CMP of 100 quality %, if the use level of aforementioned colloidal silica particles is 2.0～8.0 quality %, then this CMP will have excellent more characteristic with lapping liquid.
Content disclosed by the invention is willing to that with the special Japan of being willing to 2008-106740 number and filing an application on January 6th, 2009 of the Japan that filed an application on April 16th, 2008 is special the theme of 2009-000875 number record is associated, and their disclosure also by reference mode is quoted so far.
The invention effect
According to the present invention, the CMP that obtains grinding at a high speed interlayer dielectric uses lapping liquid, can enhance productivity through the time that shortens grinding step.
In addition, even, also can access the high grinding rate of interlayer dielectric the addition of polishing particles and comparing under few relatively situation in the past.
Further; Because few polishing particles addition also is fine, thus can be to concentrate lapping liquid than higher in the past concentration, and therefore preservation, carrying just have higher convenience; In addition, can also provide the degree of freedom higher method for using according to client's technology.
In addition; Use this CMP to carry out the Ginding process of the present invention of cmp with lapping liquid; Its productivity ratio is high, be suitable for making have excellent miniaturization, filmization, dimensional accuracy, electrical characteristic, semiconductor device that reliability is high and other electronic equipment.
Description of drawings
Fig. 1 is the schematic cross-section of general mosaic technology process; Fig. 1 (a) is that state, the Fig. 1 (b) before grinding grinds the state that distribution exposes to the barrier layer with metal (conductive material), and Fig. 1 (c) is ground to the state that the protuberance of interlayer dielectric exposes;
Fig. 2 is an example that is used to calculate the shape of particle of two average primary particle diameters;
(a)～(d) of Fig. 3 is the generalized section of an example of the formation operation of wiring layer in the semiconductor device;
Fig. 4 is the generalized section of an example after the overmastication in the 2nd grinding step.
Symbol description
1 interlayer dielectric
2 barrier layers
3 conductive materials
4 particles
5 bounding rectangles
6 substrates
7 recesses
The part of 8 overmastications
The long limit of L bounding rectangle
The minor face of B bounding rectangle
Embodiment
As previously mentioned, CMP of the present invention contains medium and is dispersed in the colloidal silica particles as polishing particles in the aforementioned medium with lapping liquid, the full terms shown in (1)～(3) below aforementioned colloidal silica particles satisfies:
(1) from the image that obtains through the aforementioned colloidal silica particles of scanning electron microscopy (SEM) observation, selects 20 particles arbitrarily, two average primary particle diameter (R of said 20 particles 1) be 35～55nm;
(2) have and two average primary particle diameter (R that in aforementioned (1), try to achieve 1) the specific area calculated value of positive spheroid of same particle size is (S 0), the specific area of the aforementioned colloidal silica particles of measuring through the BET method is (S 1), with (S 0) removal (S 1) resulting value (S 1/ S 0) be below 1.20;
(3) CMP with lapping liquid in, the aggregate particle size (Rs) through the fixed aforementioned colloidal silica particles of dynamic light scattering mode particle size distribution instrumentation, with two average primary particle diameter (R that in aforementioned (1), try to achieve 1) ratio (degree of association: Rs/R 1) be below 1.30.CMP with respect to 100 quality % uses lapping liquid, and the use level of aforementioned colloidal silica particles is preferably 2.0～8.0 quality %.
Below, at length explain with the various compositions that can contain in the lapping liquid about the meaning and the CMP of aforementioned (1)～(3).
(I. colloidal silica particles)
(two average primary particle diameters of I-i.)
As the colloidal silica that adds in lapping liquid at CMP of the present invention, be preferably the fewer cataloid of quantity that the grinding relatively better, that produce through CMP of dispersion stabilization in lapping liquid is hindered.Particularly, preferred such particle: through sem observation 20 particles arbitrarily, from resulting two average primary particle diameters of observed result be preferably more than the 35nm, below the 55nm; The colloidal silica of 40nm～50nm more preferably.If two average primary particle diameters are more than 35nm, then the grinding rate of interlayer dielectric is improved, and in addition, if below 55nm, then the dispersion stabilization in lapping liquid has the tendency that is tending towards good.
In the present invention, two average primary particle diameters are obtained according to following method.At first, (usually, solid component concentration is 5～40wt%), and it is placed in the container to measure the colloidal silica that in light water, disperses in right amount.Then, be impregnated into about 30 seconds in this container to chip, said chip is to cut into the tetragonal chip that the length of side is 2cm to the wafer that has the figure distribution.Take out aforementioned chip, move in the container that is contained with pure water, wash about 30 seconds time, dry up this chip with nitrogen., SEM observe with sample bench on, apply the accelerating voltage of 10kV to aforementioned chip bearing, observe particle, the photo of breaking forth with 100,000 times multiplying powers thereafter.From the photo that obtains, select 20 arbitrarily.
For example, be under the situation of shape of that kind as shown in Figure 2 at selected particle, particle 4 is carried out external, import rectangle (bounding rectangle 5), said rectangle is to dispose to grow the longest mode in limit.Then, do L to the long limit note of this bounding rectangle 5, the minor face note is made B, calculates (L+B)/2 and (L+B)/2 two average primary particle diameters as a particle.To 20 such operations of particles enforcement arbitrarily, be called two average primary particle diameter (R among the present invention to the mean value of the value that obtains 1).
(I-ii. degree of association)
For the colloidal silica that uses in the lapping liquid of the present invention; From the grinding rate that can access desirable interlayer dielectric and the dispersion stabilization lapping liquid excellent aspect consider; The degree of association of preferred particle is the particle below 1.30, and more preferably degree of association is the particle below 1.25.In the present invention, degree of association is the aggregate particle size (Rs) of colloidal silica particles and two average primary particle diameter (R described in aforementioned (I-i) hurdle 1) ratio, that is, and with Rs/R 1Value represent.
Here,, measure CMP in right amount and use lapping liquid about aforementioned aggregate particle size (Rs), and dilute with water as required, so that get into the scope of the desired scattered light intensity of dynamic light scattering mode particle size distribution meter, thus the modulation working sample.Next put into this working sample in the dynamic light scattering mode particle size distribution meter, obtain a D50 and the value of the D50 that obtains as average grain diameter.As the particle size distribution meter of dynamic light scattering mode, for example can enumerate Beckman Coulter, Inc. with such function! コ ー Le ダ society) model N5 type.In addition, of the back, when the perhaps concentrated preservation CMP of separatory preservation uses lapping liquid,,, can measure aggregate particle size through aforementioned gimmick modulation sample from containing the slurry of colloidal silica.
As previously mentioned, the degree of association of so-called colloidal silica is little, and the meaning is exactly that this unit cell approaches spheroid, and on the existing certain grinding object face (crystal face) of the unit cell in lapping liquid, the number that can contact is just many.That is to say, be that 1 situation and degree of association are 2 situation if consider degree of association, when the particle of equal in quality % is present in CMP with lapping liquid; Degree of association is that side of 1; With degree of association is that 2 situation is compared, because number concentration is 2 times, so more unit cell can contact crystal face.Therefore think that the grinding rate of interlayer dielectric accelerates.
In addition, it has been generally acknowledged that: approach a side of the particle of spheroid, the area that can contact abradant surface owing to 1 particle becomes big, so the grinding rate of interlayer dielectric just becomes at a high speed.
(I-iii. sphericity)
At the colloidal silica that CMP of the present invention uses in lapping liquid, preferred more near that side of the particle of spheroid.From this viewpoint, obtain the theoretical value of the specific area under the measured value of the BET specific area that obtains through mensuration and the situation that postulated particle is positive ball, with the two ratio (measured value/theoretical value.Below be called sphericity) less for necessary condition.Specifically, aforementioned sphericity is preferably below 1.20, more preferably below 1.15, further is preferably below 1.13.
The value of the aforementioned sphericity of explanation asks method below.At first, with the method on aforementioned (I-i) hurdle, from arbitrarily 20 resulting results of polishing particles, obtaining two average primary particle diameter (R that obtain through sem observation 1).
Next, use the particle with its identical material, obtain through following formula (1) and have same particle size (R 1) the theoretical value (S of specific area of the positive spheroid particle of imagination 0).
S 0=4π(R 1/2) 2/[(4/3)π(R 1/2) 3×d]……（1）
In the formula (1), R 1[m] representes aforementioned two average primary particle diameters, d [g/m 3] expression aforementioned particles density.
Aforementioned density d can enough vapor-phase replacement methods be measured, and as the real density of colloidal silica particles, can use 2.05 * 10 6[g/m 3] such value.
Next, obtain the measured value (S of the specific area of actual particle 1).As common assay method, can enumerate the BET method.It is exactly, and makes non-active gas such as solid particle surfaces physical absorption nitrogen at low temperatures, can estimate specific area from the molecular cross sectional area and the adsorbance of adsorbate.
Particularly, put into drying machine to the colloidal silica sample that about 100g is dispersed in the water, make its drying, obtain silicon dioxide granule at 150 ℃.The silicon dioxide granule that obtains about 0.4g is put into the measuring element of BET specific area measuring device, in 60 minutes time of 150 ℃ of vacuum degassings.As BET specific area measuring device; Using gases absorption type specific area pore measure of spread device is NOVA-1200 (YUASA-IONIC.Co.; Ltd. make (ユ ア サ ア イ オ ニ Network ス system)), to measure with constant volume method, said constant volume method is to use the constant volume method of nitrogen as adsorbed gas; Obtain area (Area), resulting value as the BET specific area.Carry out said determination 2 times, its mean value as the BET specific area among the present invention.
Theoretical according to BET, press under the P in certain adsorption equilibrium, molecular layer physical absorption amount v representes with following formula (2).
v=v mcP/(P s-P)(1-(P/P s)+c(P/P s))……（2）
Here, P sBe the saturated vapour pressure of measuring the adsorbate gas under the temperature, v mBe monolayer adsorbance (mol/g), c is a constant.If the distortion of (2) formula, so:
P/v(P s-P)=1/v mc+(c-1)/v mc·P/P s ……（3）
According to following formula, P/v (P s-P) to relative pressure P/P sMatch obtains straight line.For example, as the relative pressure measuring point, measure 0.1,0.2 and 0.3 this P/v (P of 3 s-P), try to achieve v from the slope and the intercept of the straight line that obtains m, v mOccupied area (m with nitrogen molecular 2) and Avogadro's number (individual/as mol) to multiply each other resulting numerical value as specific area.The summation of the surface area of the particle that is contained in the powder of per unit mass is a specific area.
The theoretical value of the specific area of the imaginary spherical particle that obtains through said method is (S 0), the measured value of the specific area of the particle of measuring through the BET method is (S 1), utilize (S 0) removal (S 1) resulting value (S 1/ S 0) obtain sphericity.
As previously mentioned; Two parameters such as average primary particle diameter, degree of association and sphericity of colloidal silica; According to colloidal silica producer's knowledge, can make through control to a certain degree and to obtain, and can obtain easily from colloidal silica producer there.In addition,, with regard to lapping liquid,, just can make up and use two or more polishing particles with regard to CMP of the present invention as long as satisfy afore-mentioned characteristics.
As previously mentioned, the sphericity of so-called colloidal silica approaches 1, and the meaning is exactly that this particle approaches spheroid, and on the existing certain grinding object face (crystal face) of the particle in lapping liquid, the area that can contact is just many.That is to say that the situation that sphericity is little is compared with the big situation of sphericity, the shape on surface is Paint Gloss, so compare with the concavo-convex tangible situation of shape, more area contact crystal face can be arranged.Therefore, it has been generally acknowledged that the grinding rate of interlayer dielectric can accelerate.
(I-iv. use level)
CMP with respect to 100 quality % uses lapping liquid, and CMP is preferably 2.0～8.0 quality % with the use level of the colloidal silica in the lapping liquid.If have the use level of the colloidal silica of afore-mentioned characteristics is more than the 2.0 quality %, and the tendency that then has is can obtain good grinding rate for interlayer dielectric; If below 8.0 quality %, then the aggegation sedimentation of particle will be more prone to control, and the result has to access good dispersion stabilization, the tendency of storage stability.In addition, the use level here is the state use level down after the state that in being modulated to the CMP grinding step, can use, when the separatory of stating after being not is preserved or the use level when concentrating preservation.
(II.CMP is with the pH of lapping liquid)
CMP of the present invention uses lapping liquid, is good at grinding interlayer dielectric at a high speed.But, for be suitable for after overmastication operation in the grinding of the barrier metal stated, the grinding rate of conductive material and barrier metal preferably also remains on good value.From such viewpoint, the pH of lapping liquid of the present invention is preferably 1.5～5.5.If pH is more than 1.5, then suppress corrosion easily to conductive material, the dish that suppresses easily to be caused because of the overmastication conductive material falls into.In addition, compare, handle easily with the situation that acidity is strong excessively.In addition, if pH is below 5.5, then also can all obtain good grinding rate for conductive material and barrier metal.
(III. medium)
As the medium of CMP with lapping liquid, have no particular limits, preferably be the medium of main component with water, more specifically, preferred deionized water, ion exchange water, ultra-pure water etc.
For lapping liquid, can add the organic solvent beyond the water for CMP as required.The cosolvent that these organic solvents can be used as the composition that is insoluble in water uses, and perhaps, also can be used to improve CMP with the wetability of lapping liquid to abradant surface.These technology are disclosed in International Publication WO03/038883 brochure, International Publication WO00/39844 brochure etc., and their disclosed contents are quoted so far by reference.As CMP of the present invention with the organic solvent in the lapping liquid, the special restriction that does not have, the organic solvent that preferably can mix with arbitrary proportion with water can use a kind or mix and use more than 2 kinds separately.
As the organic solvent when the cosolvent, can enumerate ethanol, acetate isopolarity solvent.In addition; In order to improve wetability, for example can enumerate: glycols, glycol monoether, diol bisether class, alcohols, carbonates, lactone, ethers, ketone, other phenols, dimethyl formamide, N-methyl pyrrolidone, ethyl acetate, ethyl lactate, sulfolane etc.Be preferably be selected from following at least a: glycol monoether, alcohols, carbonates.
Be combined with under the situation of organic solvent, using lapping liquid with respect to the CMP of 100 quality %, the use level of organic solvent is preferably 0.1～95 quality %, and more preferably 0.2～50 quality % is preferably 0.5～10 quality % especially.If use level is more than 0.1 quality %; Then have and obtain making the tendency of lapping liquid easily the effect of the wetability raising of substrate; If below 95 quality %, because CMP is less with the processing of the lapping liquid situation of difficult that becomes, so be preferred on manufacturing process.
In addition, the use level of water is that surplus gets final product, and has no particular limits as long as contain promptly.In addition, also can be used as diluent and use, be used for after the grinding fluid dilution of the concentrated preservation stated to the concentration that is fit to use.
(other compositions of IV.)
CMP of the present invention uses lapping liquid, and main purpose is the grinding rate that obtains for conductive material and barrier metal, can also contain the oxidant (below, abbreviate oxidant as) of oxidized metal dissolving agent, metal further.In addition, CMP with the low situation of the pH of lapping liquid under because the etching that possibly produce conductive material, so can contain corrosion inhibitor for metal for the generation that suppresses it.Below, describe about these compositions.
As being used in CMP of the present invention, be for the dissolving of the adjustment of pH and conductive material and the material that uses, if having this function then have no particular limits with the oxidized metal dissolving agent in the lapping liquid.Particularly, for example can enumerate: the salt of organic acid, organic acid esters, organic acid salt, inorganic acid, inorganic acid etc.As aforesaid salt, representational material is an ammonium salt.Wherein, from keeping practical CMP with grinding rate with suppress the viewpoint of etching speed effectively, organic acids such as formic acid, malonic acid, malic acid, tartaric acid, citric acid, salicylic acid, adipic acid are preferred.In addition, be easy to get calmly the viewpoint of the high grinding rate of conductive material is set out inorganic acids such as preferably sulfuric acid.These oxidized metal dissolving agent can use a kind perhaps to mix use more than 2 kinds separately, can also be also with aforementioned organic acid and aforementioned inorganic acid.
Be combined with under the situation of aforementioned oxidized metal dissolving agent; About its use level; Be easy to get calmly the viewpoint of the good grinding rate on conductive material, barrier layer is set out, use lapping liquid, be preferably more than the 0.001 quality % with respect to the CMP of 100 quality %; More preferably more than the 0.002 quality %, be preferably especially more than the 0.005 quality %.In addition, use level is preferably below the 20 quality %, more preferably below the 10 quality %, is preferably especially below the 5 quality %, and this is because so can have the tendency that etched inhibition is become easily and can prevent to take place on the abradant surface cracking.
As being used in CMP of the present invention with the corrosion inhibitor for metal in the lapping liquid; As long as have the ability that forms diaphragm for conductive material; Have no particular limits; Particularly, for example, can enumerate material, material, material, material, material, material, have the material of tetrazolium skeleton etc. with thiazole skeleton with guanidine skeleton with imidazoles skeleton with pyridine skeleton with pyrazoles skeleton with triazole skeleton.They can use a kind perhaps to mix use more than 2 kinds separately.
As the use level of aforementioned metal corrosion inhibitor, in order to obtain its effect, use lapping liquid with respect to the CMP of 100 quality %, be preferably more than the 0.001 quality %, more preferably more than the 0.002 quality %.In addition,, be preferably below the 10 quality %, more preferably below the 5 quality %, be preferably especially below the 2 quality % from suppressing the viewpoint of grinding rate step-down.
As being used in CMP of the present invention with the oxidant in the lapping liquid; As long as have the ability of the aforementioned conductive material of oxidation; Have no particular limits, for example can enumerate particularly: hydrogen peroxide, nitric acid, periodic acid potassium, hypochlorous acid, Ozone Water etc., wherein preferred especially hydrogen peroxide.They can use a kind perhaps to mix use more than 2 kinds separately.
When substrate is when containing integrated circuit with the silicon substrate of element,, preferably do not contain the oxidant of nonvolatile component owing to do not hope because of alkali metal, alkaline-earth metal, halide etc. cause pollution.But because the composition of Ozone Water is along with change of time is violent, so optimal be hydrogen peroxide.In addition, the matrix of application is not contain under the situation of glass substrate etc. of semiconductor element, also is fine even contain nonvolatile component.
Under the situation that cooperates aforementioned oxidant, as its use level, from obtaining viewpoint to the oxidation of metal; CMP for 100 quality % uses lapping liquid; Be preferably more than the 0.001 quality %, more preferably more than the 0.005 quality %, be preferably especially more than the 0.01 quality %.In addition, produce coarse viewpoint, be preferably below the 50 quality %, more preferably below the 20 quality %, be preferably especially below the 10 quality % from being suppressed at abradant surface.In addition, using under the situation of hydrogen peroxide as oxidant, as common hydrogen peroxide solution owing to become more readily available, so so that hydrogen peroxide finally the mode within above-mentioned scope cooperate hydrogen peroxide solution.
As explaining before this, CMP of the present invention with the very big speciality that lapping liquid has is exactly: the grinding rate for interlayer dielectric is high, and, very big as the choice of materials for polishing liquid.That is to say, in the past, in order to improve the characteristic of CMP, and when changing a kind of kind or use level of composition, have that various compositions delicate balance each other will be broken, the tendency of other deterioration in characteristics with lapping liquid.For example, change the kind time-like of composition for the flatness that improves the surface after the grinding, will cause that the grinding rate as most important factor produces the problem that reduces.
But, for lapping liquid,, be easy so assign to adjust characteristic with other one-tenth because aforesaid polishing particles improves the effect highly significant of nonferromagnetic substance (particularly grinding rate) for CMP of the present invention.For example, through changing kind as the composition of having explained of above-mentioned (other compositions of IV.), addition etc., can access various types of lapping liquids.This just means, uses known knowledge, even increase or reduce the grinding rate of conductive material or barrier metal, is affected for the grinding rate of interlayer dielectric also not conference.Therefore; Through changing other compositions; The grinding rate that obtains barrier metal is easily used lapping liquid than the grinding rate CMP high, that just selectivity is high of conductive material; On the contrary, the grinding rate that also obtains barrier metal and conductive material easily is with degree, just nonselective CMP uses lapping liquid.
Further,,, also can access the grinding rate of higher interlayer dielectric, therefore, consider it also is favourable from the cost aspect even the addition of polishing particles is less relatively according to lapping liquid of the present invention.
Certainly, under the degree that does not influence aggegation/sedimentation etc., can add polishing particles more.But, because addition also is fine less, so for example when lapping liquid being carried/preserve, can be condensed into high concentration.That is, the liquid or two liquid that contain the slurry of colloidal silica particles and contain the composition except that colloidal silica particles are separately to preserve, and when carrying out the CMP grinding step, can modulate and use through mixing them.For example, can be the CMP use lapping liquid that the use level of colloidal silica particles is modulated to respect to 100 quality % 2.0～8.0 quality %, use.
(separatory preservation)
Through containing the compositions such as oxidized metal dissolving agent of bright accordingly that kind, can adjust to preferred value to grinding rate, still, sometimes therefore can reduce the stability of polishing particles.In order to prevent the generation of this situation, lapping liquid of the present invention can be divided into like the preservation of getting off: the slurry that comprises aforementioned colloidal silica at least; The annex solution that comprises composition (for example, can reduce the composition of the dispersion stabilization of colloidal silica) in addition.For example, contain at lapping liquid under the situation of aforesaid colloidal silica, oxidized metal dissolving agent, oxidant, corrosion inhibitor for metal and water, can separate preservation to the oxidant of the dispersion stabilization that possibly influence colloidal silica and colloidal silica.
(concentrate and preserve)
CMP of the present invention is with the colloidal silica that uses in the lapping liquid, because two average primary particle diameters, degree of association and sphericities within illustrated before this scope, so have dispersed extremely excellent characteristic, can be dispersed in the medium with high concentration.Colloidal silica in the past, even adopt known method to improve dispersiveness, the amount about 10 quality % has been the limit just at the most, if add more than the scope at this, will cause the aggegation sedimentation.But CMP of the present invention is with employed colloidal silica in the lapping liquid, can be being dispersed in the medium more than the 10 quality %, can both easily be dispersed in the medium below about 12 quality %.In addition, maximum can be to disperse about 18 quality %.This just means, CMP of the present invention can carrying/preservation under highly enriched state with lapping liquid, is extremely beneficial on technology.This just means, for example uses under the situation of CMP with lapping liquid of the colloidal silica that contains 5 quality %, and is can 3 times when preservation/carrying concentrated.
More specifically; For example, be divided into the concentrated slurry that comprises aforesaid colloidal silica more than the 10 quality % at least, the annex solution that contains composition in addition, dilution, before grinding step begins, just mix them; Perhaps; With the mode of the concentration that obtains expecting, the limit is regulated the flow limit and is supplied with, and can obtain CMP thus and use lapping liquid when grinding.In addition, in dilution, also can contain the composition except that colloidal silica, for example, also can be divided into: concentrate slurry, as the hydrogen peroxide solution that contains the diluent of oxidant, contain the annex solution of composition in addition.
(V. purposes and method for using)
The lapping liquid of the present invention of above that kind can be applied to the formation of the wiring layer in the semiconductor device.For example, can be used for CMP for substrate with conductive material layer, barrier metal layer, interlayer dielectric.
Ginding process of the present invention is a kind of Ginding process that grinds substrate, and said substrate has: the interlayer dielectric that has recess and protuberance on the surface; Cover the barrier metal layer of aforementioned interlayer dielectric surfacewise; Fill the conductive material layer of aforementioned recess and covering barrier metal.This Ginding process comprises: grind the conductive material layer and make the 1st grinding step that the barrier metal of aforementioned protuberance exposes; At least grind the 2nd grinding step of the conductive material layer of barrier metal and recess.In addition, in the 2nd grinding step, after the interlayer dielectric of protuberance exposes, also can further grind the part of thickness of the protuberance of interlayer dielectric sometimes, make its planarization.In addition, use lapping liquid Yi Bian in aforementioned the 2nd grinding step, supply with aforementioned CMP of the present invention, Yi Bian carry out cmp.
As aforementioned conductive material, the oxide, tungsten, tungsten alloy, silver, gold etc. that can enumerate oxide or the copper alloy of copper, copper alloy, copper are the material of main component with the metal, preferably are the material of main component with copper.As the conductive material layer, can use through known sputtering method, plating method resulting film after the aforementioned substances film forming.
As aforementioned interlayer dielectric, can enumerate silicon based coating, organic polymer films.
As aforementioned silicon based coating, can enumerate: with silicon dioxide, fluorosilicate glass, trimethyl silane, dimethoxy dimethylsilane is silicon based coating, carborundum and silicon nitrides etc. such as the resulting organic silicate glass of initiation material, silicon oxynitride, hydrogen silsesquioxanes.
In addition, as aforementioned organic polymer films, can enumerate all aromatic low-k interlayer dielectric film.Be preferably organic silicate glass especially.These films can carry out film forming through CVD method, method of spin coating, dip coated method or spraying process.As the concrete example of dielectric film, can enumerate interlayer dielectric in the particularly multilayer wired formation operation of LSI manufacturing process etc.
Aforementioned barrier metal layer; In order to prevent that conductive material from spreading and the adaptation that improves dielectric film and conductive material forms in interlayer dielectric; The stacked film that can enumerate barrier metal and contain this barrier metal; Said barrier metal is selected from least a in the following material: tantalum, tantalum nitride, tantalum alloy, other tantalum compound, titanium, titanium nitride, titanium alloy, other titanium compound; Tungsten, tungsten nitride, tungsten alloy, other tungsten compound, ruthenium, other ruthenium compound.
As the device that grinds, for example, under the situation of grinding through grinding pad, operable general lapping device has: the anchor clamps that can keep being ground substrate; Be connected price fixing on motor that rotating speed can change etc., that be pasted with grinding pad.
As grinding pad, can use general nonwoven fabrics, polyurathamc, porous matter fluororesin etc., do not have special restriction.
Though for not restriction of grinding condition, for substrate can not fly out, the rotary speed of price fixing is preferably 200min -1Following low speed rotation.Have by the semiconductor substrate of abradant surface the grinding pressure of grinding pad is preferably 1～100kPa, in order to satisfy the uniformity of CMP speed in crystal face and the flatness of figure, more preferably 5～50kPa.
During grinding, supply with CMP continuously with lapping liquid with pump etc. and to give grinding pad.This quantity delivered is restriction not, and the surface of preferred mill pad is covered with by lapping liquid often.Preferably, the substrate after grinding finishes, after in flowing water, fully washing, feasible dropping attached to the water droplet on the substrate such as use Rotary drying make its drying then.Preferably, implement to introduce the substrate cleaning operation again according to after the cmp operation of the present invention.
Ginding process of the present invention can be applied to the formation of wiring layer in the semiconductor device for example.
Below, according to the formation of wiring layer in the semiconductor device of that kind shown in Figure 3, the execution mode of Ginding process of the present invention is described.
At first, shown in Fig. 3 (a), at interlayer dielectrics 1 such as silicon substrate 6 laminated silicon dioxide.Then, shown in Fig. 3 (b),, on the interlayer dielectric surface, form recess 7 (substrate exposed division), obtain having the interlayer dielectric of protuberance and recess with predetermined pattern through known means such as resist layer formation, etchings.Then, shown in Fig. 3 (c), on interlayer dielectric, the barrier metals such as tantalum 2 that cover interlayer dielectric, convex-concave is surfacewise carried out film forming through vapor deposition or CVD etc.
Further, shown in Fig. 3 (d), wait to form through vapor deposition, plating or CVD to cover 3 layers of conductive materials barrier metal, that constitute with metal by distributions such as copper, to fill aforementioned recess.The formation thickness of interlayer dielectric 1, barrier metal 2 and conductive material 3 is preferably 0.01～2.0 μ m, 1～100nm separately, about 0.01～2.5 μ m.
Next; As shown in Figure 1; The lapping liquid that uses the grinding rate of aforementioned conductive material/barrier metal for example to use than enough big aforementioned conductive material grinds (the 1st grinding step) through CMP for 3 layers to the conductive material on the surface of this semiconductor substrate.Thus, as Fig. 1 (b), the barrier metal of the protuberance on the substrate exposes to the surface, obtains the residual conductor fig that the expectation of aforementioned conductive material film is arranged on recess.Can be this picture surface that obtains, as use CMP of the present invention with the 2nd grinding step in the Ginding process of the present invention of lapping liquid use by abradant surface, grind.
In the 2nd grinding step, use can be ground the lapping liquid of the present invention of conductive material, barrier metal and interlayer dielectric, through cmp, grinds the conductive material of aforementioned barrier metal that exposes and recess at least.
Shown in Fig. 1 (c); The interlayer dielectric of protuberance barrier metal below all exposes, and the residual aforementioned conductive material layer that the formation wiring layer is arranged on the recess is after expose in the cross section of the boundary barrier metal of protuberance and recess; The figure that obtains expecting finishes to grind this moment.
Excellent more flatness when finishing in order to ensure grinding, further, as shown in Figure 4; (for example carry out overmastication; The needed time was 100 seconds before the figure that obtains expecting in the 2nd grinding step, in this case, except the grinding in this 100 second, appended for 50 seconds again and ground; Such grinding is called overmastication 50%), the degree of depth that is ground to the part of the interlayer dielectric that comprises protuberance also is fine.In Fig. 4, dot the part 8 of overmastication.
Passing through on the formed metal wiring of said method; Further form the metal wiring of interlayer dielectric and the 2nd layer; After forming interlayer dielectric once more between this distribution and on the distribution, grind, make the whole face of semiconductor substrate become level and smooth face.Semiconductor device (not shown) through the distribution number of plies that repeats this operation predetermined times, can make to have expectation.
CMP of the present invention uses lapping liquid; Not only can grind the silicon compound film that on the semiconductor substrate of aforementioned that kind, forms; And can be used for grinding: inorganic insulating membranes such as the silicon oxide film that on distributing board, forms, glass, silicon nitride with specific distribution; Optical glass such as photomask prism lens; Inorganic conductive films such as ITO, optics such as the end face of the optic integrated circuit light conversion element optical waveguide fiber that constitutes by glass and crystalline material, scintillator with monocrystalline, solid state laser monocrystalline, blue laser with semiconductor monocrystals such as LED sapphire substrate, SiC, GaP, GaAs, substrates such as glass substrate for disc, magnetic head.
Embodiment
Below, through embodiment the present invention is described.But the present invention is not limited to these embodiment.
(embodiment 1～3, comparative example 1～8)
(I-1) CMP is with the preparation of lapping liquid
Various material preparation CMP use lapping liquid according to following mixed: the BTA of colloidal silica A～K of 5.0 quality %, the malic acid of 0.5 quality %, 0.1 quality %, 0.5 quality % as corrosion inhibitor for metal as oxidized metal dissolving agent as polishing particles (abrasive particle) as the hydrogen peroxide of oxidant and the water of 93.9 quality %.In addition, for above-mentioned hydrogen peroxide, use 30% hydrogen peroxide solution, add by above-mentioned mix proportion.Two average primary particle diameter (R of colloidal silica A～K 1), sphericity S 1/ S 0, degree of association (Rs/R 1) respectively be worth as shown in table 1.
(I-2) the dispersion stabilization evaluation is with the preparation of CMP with lapping liquid
In order to estimate the dispersion stabilization of the polishing particles in the lapping liquid; Except changing to 12 quality % to the use level of polishing particles by 5.0 quality %; Change to the use level of water beyond the 86.9 quality % by 93.9 quality %, carry out same operation with aforementioned (I-1), preparation CMP uses lapping liquid.
(I-3) assay method of polishing particles characteristic
In addition, in the table 1, the characteristic of colloidal silica A～K is investigated according to following method.
(1) two average primary particle diameter (R 1)
At first, colloidal silica A～K, under the state that is dispersed in respectively in the light water, measure in right amount and be placed in the container.Then, be impregnated into the time about 30 seconds in this container to chip, said chip is to cut into the tetragonal chip that the length of side is 2cm to the wafer that has the figure distribution.Take out aforementioned chip, wash about 30 seconds time, dry up this chip with nitrogen with pure water., be placed on SEM to aforementioned chip observe with sample bench on, apply the accelerating voltage of 10kV, with the sem observation particle of 100,000 times of multiplying powers, the photo of breaking forth thereafter.
From the photo that obtains, select 20 particles arbitrarily.Selected particle is carried out external, import rectangle (bounding rectangle), said rectangle is to grow the rectangle that the longest mode in limit disposes.Do L to the long limit note of this bounding rectangle 5, the minor face note is made B, obtains (L+B)/2, calculates two average primary particle diameters of a particle.Should operate 20 particles enforcements arbitrarily, obtain the mean value of resulting value, as two average primary particle diameter (R 1).
(2) sphericity (S 1/ S 0)
About colloidal silica A～K, obtain the specific area (S of the colloidal silica particles of measuring through the BET method 1).That is, put into drying machine to the colloidal silica A～K that is dispersed in the water of about 100g, make its drying, obtain silicon dioxide granule at 150 ℃.Put into the silicon dioxide granule that about 0.4g obtains in the measuring element of BET specific area measuring device (NOVA-1200, YUASA-IONICS Co., Ltd. system (ユ ア サ ア イ オ ニ Network ス system)), 150 ℃ of vacuum degassings 60 minutes.Measure with constant volume method, said constant volume method is to use the constant volume method of nitrogen as adsorbed gas, obtains area (Area), resulting value as the BET specific area.Carry out said determination 2 times, its mean value as the BET specific area (S among the present invention 1).
In addition, positive spheroid of imagination, it has and two average primary particle diameter (R that in aforementioned (1), try to achieve 1) identical particle diameter, calculate the specific area of obtaining this positive spheroid, obtain S 0From through the resulting value of said method, calculate S 1/ S 0
(3) degree of association (Rs/R 1)
Lapping liquid about embodiment 1～3 and comparative example 1～8; Use utilizes particle size distribution meter (the Beckman Coulter of dynamic light scattering mode; Inc. a N5 type! the model of コ ー Le ダ society)); Obtain the mean value of the aggregate particle size in the lapping liquid of colloidal silica A～K then according to following mode, with it as Rs.That is, measure CMP in right amount and use lapping liquid, and dilute with water as required, to get into the scope of the desired scattered light intensity of particle size distribution, prepare working sample.Next, put into this working sample in the particle size distribution meter, obtain D50, the mean value (Rs) of the value that obtains as aggregate particle size.
Two average primary particle diameter (R that calculate this value and in aforementioned (1), try to achieve 1) ratio (Rs/R 1), with this as degree of association.
(II: assessment item)
(II-1: grinding rate)
The lapping liquid that use obtains in aforementioned (I-1) under following grinding condition, grinds, 3 kinds of washings have tectal substrate (has tectal substrate a～c).
(grinding condition)
Grinding, wash mill: CMP are with grinder (Applied Materials Inc (ア プ ラ イ De マ テ リ ア Le ズ) system, ProductName are MIRRA)
Grinding pad: foaming polyurethane resin
Price fixing rotating speed: 93 rev/mins
Head rotating speed: 87 rev/mins
Grinding pressure: 14kPa
The quantity delivered of lapping liquid: 200ml/min
Milling time: 60 seconds
(having tectal substrate)
Has tectal substrate (a)
Use the CVD method to be formed with the silicon substrate of thickness as the silicon dioxide of 1000nm.
Has tectal substrate (b)
Use sputtering method to be formed with the silicon substrate of thickness as the nitrogenize tantalum film of 200nm.
Has tectal substrate (c)
Use sputtering method to be formed with the silicon substrate of thickness as the copper film of 1600nm.
About grind, after the washing 3 kinds have tectal substrate, obtain grinding rate according to following method respectively.
About having tectal substrate (a), use determining film thickness device RE-3000 (big Japanese grease is made Co., Ltd.'s system) to measure the thickness before and after grinding, obtain grinding rate by this film thickness difference.
About having tectal substrate (b) and having tectal substrate (c), use metal film thickness determinator (International Electric K.K. of Hitachi system, model are VR-120/08S) to measure the thickness before and after grinding, obtain grinding rate by this film thickness difference.
The mensuration result of grinding rate is as shown in table 1.
(II-2: the dispersion stabilization evaluation)
Use lapping liquid to the dispersion stabilization evaluation of aforementioned (I-2) preparation with CMP; In 60 ℃ thermostat, take care of the time in 2 weeks respectively; Then, the polishing particles in the lapping liquid is confirmed that with visual it has or not the generation sedimentation, estimates the dispersion stabilization of the polishing particles in the lapping liquid with this.The result is shown in table 1.
(III) evaluation result
For lapping liquid, identifiablely be: dispersion stabilization is good, and interlayer dielectric can carry out high speed with the grinding rate about 90～97nm/min and grind for the CMP of the colloidal silica that has used embodiment 1～3.
Relative therewith, in comparative example 1～8, colloidal silica particles is not character (1)～(3) of satisfying the particle of regulation simultaneously.Some is good for their dispersion stabilization, and some is not good, and the grinding rate of interlayer dielectric is approximately about 40～70nm/min.
Table 1
Figure BDA00001832398600201
(CMP of embodiment 1 is with the research of the polishing particles amount of lapping liquid)
Change to 3.0 quality % to the CMP of the colloidal silica that has used embodiment 1 with the use level of the polishing particles of lapping liquid by 5.0 quality %; Change to 96.9 quality % to the use level of water by 93.9 quality %; In addition; Implement same operation with aforementioned (I-1), CMP is with lapping liquid (embodiment 4) in preparation.In addition, change to 7.0 quality % to the use level of polishing particles by 5.0 quality %, change to 90.9 quality % to the use level of water by 93.9 quality %, in addition, implement same operation with aforementioned (I-1), CMP is with lapping liquid (embodiment 5) in preparation.
Estimate 2 above-mentioned liquid to having the tectal substrate of silicon dioxide (a), have the tectal substrate of tantalum nitride (b), having the grinding rate of the substrate (c) of copper capping layer with above-mentioned evaluation method.Its result is shown in Table 2 with the result of embodiment 1.
Can confirm that from table even change the polishing particles use level of the CMP of embodiment 1 with lapping liquid to a certain extent, the grinding rate of interlayer dielectric also is about 81～102nm/min, compares with comparative example 1～8, be to grind at a high speed.
[table 2]
Utilizability on the industry
According to the present invention, the CMP that can obtain grinding at a high speed interlayer dielectric uses lapping liquid, can enhance productivity through shortening the grinding step time.
In addition, though the addition of polishing particles with before to compare be under the less relatively situation, also can access high interlayer dielectric grinding rate.
Further, owing to few polishing particles addition gets final product, therefore can be to concentrate lapping liquid than higher in the past concentration, therefore preservation, carrying just have higher convenience, in addition, can also provide the degree of freedom higher method for using according to client's technology.
In addition; Use this CMP to carry out the Ginding process of the present invention of cmp with lapping liquid; Its productivity ratio is high, be suitable for making have excellent miniaturization, filmization, dimensional accuracy, electrical characteristic, semiconductor device that reliability is high and other electronic equipment thereof.

Claims (2)

1. a CMP is with the application of lapping liquid; It is characterized in that; Said CMP is used for grinding that the part of the barrier metal of substrate and interlayer dielectric is removed with lapping liquid; Said substrate has: the layer of the said barrier metal that have the said interlayer dielectric of recess and protuberance on the surface, said interlayer dielectric is covered surfacewise, fill said recess and cover the conductive material layer of said barrier metal
Said CMP contains medium and is dispersed in the colloidal silica particles in the said medium with lapping liquid, the condition of (1)～(3) below said colloidal silica particles satisfies:
(1) from the image that obtains through the said colloidal silica particles of sem observation, selects 20 particles arbitrarily, two average primary particle diameter (R of said 20 particles 1) be 35～55nm;
(2) have and two average primary particle diameter (R that in said (1), try to achieve 1) the specific area calculated value of positive spheroid of same particle size is S 0, the specific area of the said colloidal silica particles of measuring through the BET method is S 1, use S 0Remove S 1Resulting value S 1/ S 0Be below 1.20;
(3) CMP with lapping liquid in, through the aggregate particle size (Rs) of the fixed said colloidal silica particles of dynamic light scattering mode particle size distribution instrumentation and two average primary particle diameter (R that in said (1), try to achieve 1) ratio (degree of association: Rs/R 1) be below 1.30.
2. a CMP is characterized in that with the application of lapping liquid, and said CMP is used for comprising said the 2nd grinding step of the Ginding process of the 1st grinding step and the 2nd grinding step with lapping liquid,
Said the 1st grinding step makes the operation that the barrier metal of protuberance exposes for the conductive material layer that grinds substrate; Said substrate has: the layer of the said barrier metal that have the interlayer dielectric of recess and said protuberance on the surface, said interlayer dielectric is covered surfacewise, fill said recess and cover the said conductive material layer of said barrier metal
Said the 2nd grinding step is the operation of grinding the conductive material layer of barrier metal and recess at least,
Said CMP contains medium and is dispersed in the colloidal silica particles in the said medium with lapping liquid, the condition of (1)～(3) below said colloidal silica particles satisfies:
(1) from the image that obtains through the said colloidal silica particles of sem observation, selects 20 particles arbitrarily, two average primary particle diameter (R of said 20 particles 1) be 35～55nm;
(2) have and two average primary particle diameter (R that in said (1), try to achieve 1) the specific area calculated value of positive spheroid of same particle size is S 0, the specific area of the said colloidal silica particles of measuring through the BET method is S 1, use S 0Remove S 1Resulting value S 1/ S 0Be below 1.20;
(3) CMP with lapping liquid in, through the aggregate particle size (Rs) of the fixed said colloidal silica particles of dynamic light scattering mode particle size distribution instrumentation and two average primary particle diameter (R that in said (1), try to achieve 1) ratio (degree of association: Rs/R 1) be below 1.30.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655867A (en) * 2018-06-28 2020-01-07 凯斯科技股份有限公司 Polishing slurry composition

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100291840A1 (en) * 2009-05-12 2010-11-18 Taiwan Semiconductor Manufacturing Co., Ltd. System and method for conditioning chemical mechanical polishing apparatus using multiple conditioning disks
WO2013039750A1 (en) * 2011-09-15 2013-03-21 Planar Solutions, Llc Homogeneous blending
TWI453273B (en) * 2011-11-07 2014-09-21 Uwiz Technology Co Ltd Slurry composition and use thereof
US20140302753A1 (en) * 2011-11-08 2014-10-09 Fujimi Incorporated Polishing composition
KR20150008442A (en) * 2012-05-07 2015-01-22 바스프 에스이 Process for manufacture of semiconductor devices
WO2014069139A1 (en) * 2012-11-02 2014-05-08 株式会社フジミインコーポレーテッド Polishing composition
US9309442B2 (en) * 2014-03-21 2016-04-12 Cabot Microelectronics Corporation Composition for tungsten buffing
WO2016032145A1 (en) * 2014-08-26 2016-03-03 주식회사 케이씨텍 Polishing slurry composition
KR101660384B1 (en) * 2014-10-30 2016-09-27 주식회사 케이씨텍 Polishing slurry composition
KR101854499B1 (en) 2015-04-24 2018-05-04 삼성에스디아이 주식회사 Cmp slurry composition for copper wire and polishing method using the same
JP6377656B2 (en) 2016-02-29 2018-08-22 株式会社フジミインコーポレーテッド Silicon substrate polishing method and polishing composition set
JP6699292B2 (en) * 2016-03-29 2020-05-27 日立化成株式会社 Method for producing airgel composite
JPWO2018012173A1 (en) * 2016-07-15 2019-05-30 株式会社フジミインコーポレーテッド Polishing composition, method for producing polishing composition, and polishing method
US20190292407A1 (en) * 2016-07-15 2019-09-26 Fujimi Incorporated Polishing composition, method for producing polishing composition, and polishing method
JP6846193B2 (en) * 2016-12-26 2021-03-24 ニッタ・デュポン株式会社 Polishing slurry
CN108061737A (en) * 2017-12-06 2018-05-22 北京工业大学 A kind of preparation method of the electron backscatter diffraction sample of tin-based solder interconnection solder joint
WO2020091242A1 (en) * 2018-10-31 2020-05-07 영창케미칼 주식회사 Slurry composition for polishing copper barrier layer
JP7453874B2 (en) * 2020-07-30 2024-03-21 芝浦メカトロニクス株式会社 Substrate processing method and substrate processing apparatus
KR20220109659A (en) 2021-01-29 2022-08-05 에스케이실트론 주식회사 Fimal polishing apparatus
KR102620964B1 (en) 2021-07-08 2024-01-03 에스케이엔펄스 주식회사 Polishing composition for semiconductor process and manufacturing method for polished object
CN117047653A (en) * 2022-05-06 2023-11-14 长鑫存储技术有限公司 Chemical mechanical polishing process and apparatus

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW459029B (en) * 1999-09-20 2001-10-11 Fujimi Inc Polishing composition and polishing process
TW527660B (en) * 2000-08-21 2003-04-11 Toshiba Corp Slurry for chemical mechanical polishing and manufacturing method of semiconductor device
US20070232068A1 (en) * 2006-03-29 2007-10-04 Gaku Minamihaba Slurry for touch-up CMP and method of manufacturing semiconductor device
WO2007123235A1 (en) * 2006-04-24 2007-11-01 Hitachi Chemical Co., Ltd. Polishing liquid for cmp and method of polishing
JP2008034818A (en) * 2006-07-05 2008-02-14 Hitachi Chem Co Ltd Polishing solution for polishing noble metal films and polishing method of noble metal films

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4944836A (en) * 1985-10-28 1990-07-31 International Business Machines Corporation Chem-mech polishing method for producing coplanar metal/insulator films on a substrate
US4954142A (en) * 1989-03-07 1990-09-04 International Business Machines Corporation Method of chemical-mechanical polishing an electronic component substrate and polishing slurry therefor
JP3397501B2 (en) * 1994-07-12 2003-04-14 株式会社東芝 Abrasive and polishing method
JPH08153780A (en) * 1995-04-24 1996-06-11 Mitsubishi Materials Shilicon Corp Semiconductor substrate
JP2000306873A (en) * 1999-04-20 2000-11-02 Tokuyama Corp Polishing
JP4253141B2 (en) 2000-08-21 2009-04-08 株式会社東芝 Chemical mechanical polishing slurry and semiconductor device manufacturing method
JP2002338232A (en) * 2001-05-18 2002-11-27 Nippon Chem Ind Co Ltd Secondary flocculated colloidal silica, method for producing the same and abrasive composition using the same
JP2005136134A (en) * 2003-10-30 2005-05-26 Sumitomo Bakelite Co Ltd Abrasive composition
KR20080022235A (en) * 2004-04-12 2008-03-10 히다치 가세고교 가부시끼가이샤 Metal polishing liquid and polishing method using it
JP2006147993A (en) * 2004-11-24 2006-06-08 Hitachi Chem Co Ltd Polishing solution for cmp and polishing method
JP2007012679A (en) * 2005-06-28 2007-01-18 Asahi Glass Co Ltd Abrasive and manufacturing method of semiconductor integrated circuit device
JP2007242839A (en) * 2006-03-08 2007-09-20 Adeka Corp Abrasive compound for metal chemical mechanical polishing
JP2008016678A (en) * 2006-07-06 2008-01-24 Mitsui Chemicals Inc Composition for polishing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW459029B (en) * 1999-09-20 2001-10-11 Fujimi Inc Polishing composition and polishing process
TW527660B (en) * 2000-08-21 2003-04-11 Toshiba Corp Slurry for chemical mechanical polishing and manufacturing method of semiconductor device
US20070232068A1 (en) * 2006-03-29 2007-10-04 Gaku Minamihaba Slurry for touch-up CMP and method of manufacturing semiconductor device
WO2007123235A1 (en) * 2006-04-24 2007-11-01 Hitachi Chemical Co., Ltd. Polishing liquid for cmp and method of polishing
JP2008034818A (en) * 2006-07-05 2008-02-14 Hitachi Chem Co Ltd Polishing solution for polishing noble metal films and polishing method of noble metal films

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110655867A (en) * 2018-06-28 2020-01-07 凯斯科技股份有限公司 Polishing slurry composition
US11279851B2 (en) 2018-06-28 2022-03-22 Kctech Co., Ltd. Polishing slurry composition

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